The present invention relates to a silver halide photographic emulsion and to a silver halide photographic material that contains the emulsion. More precisely, the invention relates to a silver halide photographic emulsion of good dissolution-storage stability, and to a silver halide photographic material that contains the emulsion, having the advantages that its sensitivity is high, its graininess is good, it is free from residual color even when processed rapidly, and its storage stability is good.
It is known that sensitizing dyes for spectral sensitization of silver halide photographic materials have significant influences on the properties of the materials containing them. For example, some mere difference in the structure of sensitizing dyes may have significant influences on the photographic properties such as sensitivity, fog, storage stability, residual color after processed and graininess of photographic materials that contain any of such sensitizing dyes. Combining at least two different types of sensitizing dyes to be in photographic materials also has significant influences on the photographic properties of the materials. However, it is difficult to forecast the results of the sensitizing dyes used in photographic materials. Heretofore, accordingly, many scholars have produced many different types of sensitizing dyes and have tried many their combinations for investigating their influences on the photographic properties of photosensitive materials that contain any of them or their combinations. At present, however, it is still impossible to accurately forecast the influences of different types of sensitizing dyes on the photographic properties of photosensitive materials that contain any of them.
The recent tendency in the art is toward photographic materials of high sensitivity capable of forming high-quality images, while, on the other hand, it is much desired to rapidly process photographic materials and to reduce processing wastes so as not to cause environmental pollution. In particular, a technique of spectral sensitization of silver halide grains in photographic materials is being more and more important for making them have an increased sensitivity with no defects of fog and residual color in the processed photographic materials.
Tabular photographic grains are preferred for spectral sensitization, since they have a large surface area (specific surface area) relative to their volume and can therefore adsorb a larger amount of sensitizing dye molecules. Therefore, tabular grains are effective for improving the ratio of sensitivity/graininess of photographic materials containing them. After processed, however, color-sensitized tabular grains leave much residual color in the processed materials, and the problem of residual color from color-sensitized tabular grains is more serious than that from color-sensitized regular grains.
On the other hand, it is desired to shorten the time for processing photographic materials. However, when color-sensitized photographic materials are processed rapidly within a short period of time, then the amount of the sensitizing dye that remains in the processed emulsion increases and the problem of residual color in the rapidly processed photographic materials is more serious. Accordingly, a technique of reducing residual color in processed photographic materials is much desired in the art of photography.
Regarding the means of solving the problem of residual color in processed photographic materials, it is known that sensitizing dyes of increased hydrophilicity are effective for solving the problem. In general, however, sensitizing dyes of higher hydrophilicity are more poorly adsorbed by silver halide grains, and their negative influences on the photographic properties of the silver halide grains that have poorly adsorbed them are inevitable in that the sensitivity of the silver halide grains could not be increased so much. Accordingly, the ability of such sensitizing dyes of increased hydrophilicity to solve the problem of residual color in processed photographic materials is limited.
On the other hand, when a large amount of sensitizing dye is added to tabular silver halide grains, the grains adsorb many dye molecules and the dye molecules cover the grains to a great extent. Thus much covering the tabular grains, the sensitizing dye molecules detract from the protective colloidal property of gelatin around the tabular grains. Of the tabular grains, in particular, those having a higher aspect ratio readily contact with each other at their main face to aggregate into large aggregates. Accordingly, it has been clarified that, while the emulsion is dissolved in time, there occur various side effects of fog increase, sensitivity reduction and graininess reduction. To solve the problem, for example, there is known a method of adding an emulsion of substantially insoluble fine silver iodobromide grains to the tabular silver halide grain. emulsion while or after the tabular silver halide grain emulsion is chemically sensitized; as in JP-A 6-332091 (The term xe2x80x9cJP-Axe2x80x9d as used herein means an unexamined published Japanese Patent Applicationxe2x80x9d). However, this method is not always applicable to any and every emulsion. For example, it could not be applied to a silver chloride-rich emulsion (i.e., a high silver chloride emulsion). Therefore, any other method substitutable for it is desired.
The object of the present invention is to provide a silver halide photographic emulsion of good dissolution-storage stability, and to provide a silver halide photographic material that contains the emulsion, having the advantages that its sensitivity is high, its graininess is good, it is free from residual color even when processed rapidly, and its shelf life is good.
Having assiduously studied, the present inventors have found that the object matter of the present invention can be attained by the following:
(1) A silver halide photographic material comprising a support having thereon at least one silver halide photographic emulsion layer, wherein the emulsion layer contains at least one compound selected from the group consisting of compounds represented by formulae (Ia), (Ib) and (Ic) and at least one compound represented by formula (II): 
In formulae (Ia) (Ib) and (Ic), Z1 represents a sulfur, oxygen, selenium, tellurium, nitrogen or carbon atom; R represents an optionally-substituted alkyl, aryl or heterocyclic group; D represents a group necessary for forming the methine dye; V1, V2, V3 and V4 each represent a hydrogen atom or a monovalent substituent; M represents a charge-balancing counter ion; and m indicates a number of 0 or more necessary for neutralizing the charge of the molecule. 
In formula (II), Z31 and Z32 each represent an atomic group necessary for forming the nitrogen-containing hetero-ring that may be optionally condensed with any other ring and may be optionally substituted; R31 and R32 each represent an alkyl, aryl or heterocyclic group; L31, L32, L33, L34, L35, L36 and L37 each represent a methine group; p31 and p32 each indicate 0 or 1; n3 indicates 0, 1, 2, 3 or 4; M3 represents a charge-balancing counter ion; m3 indicates a number of 0 or more necessary for neutralizing the charge of the molecule; but the compound of formula (II) does not include the compounds of formulae (Ia), (Ib) and (Ic).
(2) The silver halide photographic material of above (1), wherein D in formulae (Ia), (Ib) and (Ic) is a group necessary for forming a merocyanine dye or a cyanine dye.
(3) The silver halide photographic material of above (1), wherein D in formulae (Ia), (Ib) and (Ic) is a group necessary for forming a cyanine dye.
(4) The silver halide photographic material of any of above (1) to (3), wherein D in formulae (Ia), (Ib) and (Ic) is D1 represented by the following formula: 
In D1, R12 represents an alkyl, aryl or heterocyclic group; z11 represents an atomic group necessary for forming the nitrogen-containing hetero-ring that may be optionally condensed with any other ring and may be optionally substituted; L11, L12, L13, L14 and L15 each represent a methine group; p1 indicates 0 or 1; and nxe2x80x2 indicates 0, 1, 2, 3 or 4.
(5) The silver halide photographic material of any of above (1) to (3), wherein D in formulae (Ia), (Ib) and (Ic) is D2 represented by the following formula: 
In D2, R22 represents an alkyl, aryl or heterocyclic group; X22 represents a sulfur, oxygen, selenium, tellurium, nitrogen or carbon atom; V21, V22, V23 and V24 each represent a hydrogen atom or a substituent, provided that the two adjacent substituents do not bond to each other to form a saturated or unsaturated condensed ring; L21, L22 and L23 each represent a methine group; and n2 indicates 0, 1, 2, 3 or 4.
(6) The silver halide photographic material of any of above (1) to (5), wherein R in formulae (Ia), (Ib) and (Ic) is an alkyl group substituted with an acid group.
(7) The silver halide photographic material of any of above (1) to (6), wherein the emulsion layer contains at least one compound of formula (Ia) or (Ib) and at least one compound of formula (II).
(8) The silver halide photographic material of any of above (1) to (7), wherein V1, V2, V3 and V4 in formulae (Ia), (Ib) and (Ic) are all hydrogen atoms.
(9) The silver halide photographic material of any of above (1) to (8), wherein the compounds of formula (II) are selected from the group consisting of compounds represented by formula (IIa): 
In formula (IIa), X41 and X42 each represent a sulfur, oxygen, selenium, tellurium, nitrogen or carbon atom; V41, V42, V43, V44, V45, V46, V47 and V48 each represent a hydrogen atom or a substituent, provided that the two adjacent substituents may bond to each other to form a saturated or unsaturated condensed ring; R41 and R42 each represent an alkyl, aryl or heterocyclic group; L41, L42 and L43 each represent a methine group; n4 indicates 0, 1, 2, 3 or 4; M4 represents a counter ion; and m4 indicates a number of 0 or more necessary for neutralizing the charge of the molecule.
(10) The silver halide photographic material of any of above (1) to (8), wherein the compounds of formula (II) are selected from the group consisting of compounds represented by formula (III) and (IV): 
In formula (III), X51 and X52 each represent an oxygen or sulfur atom; V51, V52, V53, V54, V55 and V56 each represent a hydrogen atom or a substituent, provided that the two adjacent substituents do not bond to each other to form a saturated or unsaturated condensed ring; R51, R52 and R53 each represent an alkyl, aryl or heterocyclic group; M5 represents a counter ion; and m5 indicates a number of 0 or more necessary for neutralizing the charge of the molecule. 
In formula (IV), X61 represents an oxygen or sulfur atom: V61, V63, V64, V65 and V66 each represent a hydrogen atom or a substituent, provided that the two adjacent substituents do not bond to each other to form a saturated or unsaturated condensed ring; R61 and R62 each represent an alkyl, aryl or heterocyclic group; M6 represents a counter ion; and m6 indicates a number of 0 or more necessary for neutralizing the charge of the molecule.
(11) The silver halide photographic material of any of above (1) to (10), wherein tabular grains having an aspect ratio of at least 2 account for at least 50% of the overall projected area of all the silver halide grains in the emulsion.
(12) The silver halide photographic material of any of above (1) to (11), wherein the emulsion for the emulsion layer is sensitized with selenium.
(13) The silver halide photographic material of any of above (1) to (12), wherein silver chloride accounts for at least 95 mol % of the emulsion for the emulsion layer.
(14) The silver halide photographic material of any of above (1) to (12), wherein silver bromide accounts for at least 95 mol % of the emulsion for the emulsion layer.
The present invention is described in detail hereinunder.
The xe2x80x9cgroupxe2x80x9d referred to herein means a specific part of a compound, and it may be or may not be substituted by itself with at least one (and up to a possible largest number) of substituents. For example, the xe2x80x9calkyl groupxe2x80x9d means a substituted or unsubstituted alkyl group. The substituent that may be in the compound in the present invention may be of any and every possible one, and may be or may not be further substituted with any other substituent.
The substituent will be represented by V. The substituent for V may be any and every one, not specifically defined. Example thereof includes a halogen atom, an alkyl group [including a cycloalkyl group, a bicycloalkyl group and a tricycloalkyl group, further including an alkenyl group (naturally including a cycloalkenyl group and a bicycloalkenyl group) and an alkynyl group] , an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group, an aryloxy group, a silyloxy group, a heterocyclic-oxy group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an amino group (including an anilino group), an ammonio group, an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoylamino group, an alkyl or arylsulfonylamino group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclic-thio group, a sulfamoyl group, a sulfo group, an alkyl or arylsulfinyl group, an alkyl or arylsulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an aryl or heterocyclic-azo group, an imido group, a phosphino group, a phosphinyl group, a phosphinyloxy group, aphosphinylamino group, aphosphono group, a silyl group, ahydrazino group, anureido group, aboronic acid group (xe2x80x94B(OH)2), a phosphato group (xe2x80x94OPO(OH)2), a sulfato group (xe2x80x94OSO3H), and other known substituents.
More precisely, V includes a halogen atom (e.g., fluorine, chlorine, bromine and iodine atoms), an alkyl group [it is a linear, branched or cyclic, substituted or unsubstituted alkyl group, and includes, for example, an alkyl group (preferably an alkyl group having from 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl and 2-ethylhexyl), a cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having from 3 to 30 carbon atoms, e.g., cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having from 5 to 30 carbon atoms, or that is, a monovalent group derived from a bicycloalkane having from 5 to 30 carbon atoms by removing one hydrogen atom from it; for example, this includes bicyclo[1,2,2]heptan-2-yl, bicyclo [2,2,2]octan-3-yl, and others having a tricyclo or more multi-cyclo structurexe2x80x94the alkyl group in the substituents mentioned below (for example, the alkyl moiety of alkylthio group) shall indicate the alkyl group of that conception, but shall further include an alkenyl group and an alkynyl group], an alkenyl group [this indicates a linear, branched or cyclic, substituted or unsubstituted alkenyl group, and includes an alkenyl group (preferably a substituted or unsubstituted alkenyl group having from 2 to 30 carbon atoms, e.g., vinyl, allyl, prenyl, geranyl, oleyl), acycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having from 3 to 30 carbon atoms, or that is, a monovalent group derived from a cycloalkene having from 3 to 30 carbon atoms by removing one hydrogen atom from itxe2x80x94for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), a bicycloalkenyl group (a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having from 5 to 30 carbon atoms, or that is, a monovalent group derived from a bicycloalkene having at least one double bond by removing one hydrogen atom from itxe2x80x94for example, bicyclo[2,2,1]hept-2-en-1-yl, bicyclo[2,2,2]oct-2-en-4-yl)], an alkynyl group (preferably a substituted or unsubstituted alkynyl group having from 2 to 30 carbon atoms, e.g., ethynyl, propargyl, trimethylsilylethynyl), an aryl group (preferably a substituted or unsubstituted aryl group having from 6 to 30 carbon atoms, e.g., phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), a heterocyclic group (preferably a monovalent group derived from a 5-membered or 6-membered, substituted or unsubstituted, aromatic or non-aromatic heterocyclic compound by removing one hydrogen atom from it, more preferably a 5-membered or 6-membered aromatic heterocyclic group having from 3 to 30 carbon atoms, e.g., 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl, as well as other cationic heterocyclic groups such as 1-methyl-2-pyridinio and 1-methyl-2-quinolinio groups), a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group (preferably a substituted or unsubstituted alkoxy group having from 1 to 30 carbon atoms, e.g., methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy), an aryloxy group (preferably a substituted or unsubstituted aryloxy group having from 6 to 30 carbon atoms, e.g., phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), a silyloxy group (preferably a silyloxy group having from 3 to 20 carbon atoms, e.g., trimethylsilyloxy, t-butyldimethylsilyloxy), a heterocyclic-oxy group (preferably a substituted or unsubstituted heterocyclic-oxy group having from 2 to 30 carbon atoms, e.g., 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), an acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having from 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having from 6 to 30 carbon atoms, e.g., formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having from 1 to 30 carbon atoms, e.g., N,N-dimethylcarbamoyloxy, N,N-diethylcarbamoyloxy, morpholinocarbonyloxy, N,N-di-n-octylaminocarbonyloxy, N-n-octylcarbamoyloxy), an alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having from 2 to 30 carbon atoms, e.g., methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octyloxycarbonyloxy), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyl oxy group having from 7 to 30 carbon atoms, e.g., phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, p-n-hexadecyloxyphenoxycarbonyloxy), an amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having from 1 to 30 carbon atoms, a substituted or unsubstituted anilino group having from 6 to 30 carbon atoms, e.g., amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino), an ammonio group (preferably an ammonio group, an ammonio group substituted with a substituted or unsubstituted alkyl, aryl or heterocyclic group having from 1 to 30 carbon atoms, e.g., trimethylammonio, triethylamonio, diphenylmethlylammonio), an acylamino group (preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having from 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having from 6 to 30 carbon atoms, e.g., formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), an aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonyl amino group having from 1 to 30 carbon atoms, e.g., carbamoylamino, N,N-dimethylaminocarbonylamino, N,N-diethylaminocarbonylamino, morpholinocarbonylamino), an alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having from 2 to 30 carbon atoms, e.g., methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino), an aryloxycarbonylamino group (e.g., a substituted or unsubstituted aryloxycarbonylamino group having from 7 to 30 carbon atoms, e.g., phenoxycarbonylamino, p-chlorophenoxycarbonylamino, m-n-octyloxyphenoxycarbonylamino), a sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having from 0 to 30 carbon atoms, e.g., sulfamoylamino, N,N-dimethylaminosulfonylamino, N-n-octylaminosulfonylamino), an alkyl or arylsulfonylamino group (preferably a substituted or unsubstituted alkylsulfonylamino group having from 1 to 30 carbon atoms, or a substituted or unsubstituted arylsulfonylamino group having from 6 to 30 carbon atoms, e.g., methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), a mercapto group, an alkylthio group (preferably a substituted or unsubstituted alkylthio group having from 1 to 30 carbon atoms, e.g., methylthio, ethylthio, n-hexadecylthio), an arylthio group (preferably a substituted or unsubstituted arylthio group having from 6 to 30 carbon atoms, e.g., phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic-thio group (preferably a substituted or unsubstituted heterocyclic-thio group having from 2 to 30 carbon atoms, e.g., 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having from 0 to 30 carbon atoms, e.g., N-ethylsulfamoyl, N-(3-dodecyloxypropyl)sulfamoyl, N,N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N-(Nxe2x80x2-phenylcarbamoyl)sulfamoyl), a sulfo group, an alkyl or arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having from 1 to 30 carbon atoms, or a substituted or unsubstituted arylsulfinyl group having from 6 to 30 carbon atoms, e.g., methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl), an alkyl or arylsulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having from 1 to 30 carbon atoms, or a substituted or unsubstituted arylsulfonyl group having from 6 to 30 carbon atoms, e.g., methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), an acyl group (preferably a formyl group, a substituted or unsubstituted alkylcarbonyl group having from 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having from 7 to 30 carbon atoms, or a substituted or unsubstituted heterocyclic-carbonyl group having from 4 to 30 carbon atoms and bonding to the carbonyl group via its carbon atom, e.g., acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, p-n-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl), an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having from 7 to 30 carbon atoms, e.g., phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, p- t-butylphenoxycarbonyl), an alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having from 2 to 30 carbon atoms, e.g., methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), a carbamoyl group (preferably a substituted or unsubstituted carbamoyl group having from 1 to 30 carbon atoms, e.g., carbamoyl, N-methylcarbamoyl, N,N-dimethylcarbamoyl, N,N-di-n-octylcarbamoyl, N-(methylsulfonyl)carbamoyl), an aryl or heterocyclic-azo group (preferably a substituted or unsubstituted arylazo group having from 6 to 30 carbon atoms, or a substituted or unsubstituted heterocyclic-azo group having from 3 to 30 carbon atoms, e.g., phenylazo, p-chlorophenylazo, 5-othylthio-1,3,4-thiadiazol-2-ylazo), an imido group (preferably N-succinimido, N-phthalimido), a phosphino group (preferably a substituted or unsubstituted phosphino group having from 2 to 30 carbon atoms, e.g., dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), a phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having from 2 to 30 carbon atoms, e.g., phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl), a phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having from 2 to 30 carbon atoms, e.g., diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), a phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino group having from 2 to 30 carbon atoms, e.g., dimethoxyphosphinylamino, dimethylaminophosphinylamino), a phospho group, a silyl group (preferably a substituted or unsubstituted silyl group having from 3 to 30 carbon atoms, e.g., trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl), a hydrazino group (preferably a substituted or unsubstituted hydrazino group having from 0 to 30 carbon atoms, e.g., trimethylhydrazino), an ureido group (preferably a substituted or unsubstituted ureido group having from 0 to 30 carbon atoms, e.g., N,N-dimethylureido).
Two V""s may together form a ring (e.g., aromatic or non-aromatic hydrocarbon rings, or heterocyclic ringsxe2x80x94these rings may bond to each other to form polycyclic condensed rings; for example, the rings include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolidine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thianthrene ring, chromene ring, xanthene ring, phenoxazine ring, phenothiazine ring, phenazine ring).
Of the above-mentioned substituents V""s, those having a hydrogen atom may be further substituted at its hydrogen atom with any of the above-mentioned substituents. Examples of such substituents are xe2x80x94CONHSO2xe2x80x94 (sulfonylcarbamoyl, carbonylsulfamoyl), xe2x80x94CONHCOxe2x80x94 (carbonylcabamoyl), xe2x80x94SO2NHS2xe2x80x94 (sulfonylsulfamoyl).
More concretely, they include an alkylcarbonylaminosulfonyl group (e.g., acetylaminosulfonyl), an arylcarbonylaminosulfonyl group (e.g., benzoylaminosulfonyl), an alkylsulfonylaminocarbonyl group (e.g., methylsulfonylaminocarbonyl), an arylsulfonylaminocarbonyl group (e.g., p-methylphenylaulfonylaminocarbonyl).
Methine dyes of formulae (Ia), (Ib) and (Ic) for use in the present invention are described in detail hereinunder. The groups of Z1, R, D, V1, V2, V3, V4, M and m may have the same or different meanings as in these formulae (Ia), (Ib) and (Ic).
Of the dyes of formulae (Ia), (Ib) and (Ic), preferred are those of formulae (Ia) and (Ib).
Z1 represents a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a nitrogen atom (Nxe2x80x94Va), or a carbon atom (CVbVc). Va, Vb and Vc each represent a hydrogen atom, or a substituent (e.g., V mentioned above), but are preferably any of a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. For the alkyl group, the aryl group and the heterocyclic group for these, referred to are those to be mentioned herein under for R. For these, preferred are the same groups as those for R. More preferably, these Va, Vb and Vc are alkyl groups.
Preferably, Z1 is a sulfur, oxygen, selenium or nitrogen atom, more preferably a sulfur, oxygen or selenium atom, even more preferably a sulfur or oxygen atom, most preferably a sulfur atom.
R represents an alkyl, aryl or heterocyclic group, but is preferably an alkyl or aryl group, more preferably an alkyl group. Concretely, the alkyl, aryl and heterocyclic groups for R include, for example, an unsubstituted alkyl group having from 1 to 18, preferably from 1 to 7, more preferably from 1 to 4 carbon atoms (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), a substituted alkyl group having from 1 to 18, preferably from 1 to 7, more preferably from 1 to 4 carbon atoms (for example, it is an alkyl group substituted with V mentioned above, preferably an alkyl group having an acid group such as that mentioned above; concretely, it includes an aralkyl group (e.g., benzyl, 2-phenylethyl), an unsaturated hydrocarbon group (e.g., allyl and vinyl, that is, the substituted alkyl group shall include an alkenyl group and an alkynyl group), a hydrosyalkyl group (e.g., 2-hydroxyethyl, 3-hydroxypropyl), a carboxyalkyl group (e.g., 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, carboxymethyl), an alkoxyalkyl group (e.g., 2-methoxyethyl, 2-(2-metboxyethoxy)ethyl), an aryloxyalkyl group (e.g., 2-phenoxyethyl, 2-(1-naphthoxy; ethyl), an alkoxycarbonylalkyl group (e.g., ethoxycarbonylmethyl, 2-benzyloxycarbonylethyl), anaryloxycarbonylalkyl group (e.g., 3-phenoxycarbonylpropyl), an acyloxyalkyl group (e.g., 2-acetyloxyethyl), an acylalkyl group (e.g., 2-acetylethyl), a carbamoylalkyl group (e.g., 2-morpholinocarbonylethyl), a sulfamoylalkyl group (e.g., N,N-dimethylsulfamoylmethyl), a sulfoalkyl group (e.g., 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2-(3-sulfoppropoxy)ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl), a sulfoalkenyl group, a sulfatoalkyl group (e.g., 2-sulfatoethyl, 3-sulfatopropyl, 4-sulfatobutyl), a heterocyclic group-substituted alkyl group (e.g., 2-(pyrrolidin-2-on-1-yl)ethyl, tetrahydrofurfuryl), an alkylsulfonylcarbamoylalkyl group (e.g., methanesulfonylcarbamoylmethyl), an acylcarbamoylalkyl group (e.g., acetylcarbamoylmethyl), an acylsulfamoylalkyl group (e.g., acetylsulfamoylmethyl), analkylsulfonylsulfamoylalkyl group (e.g., methanesulfonylsulfamoylmethyl)}, a substituted or unsubstituted aryl group having from 6 to 20, preferably from 6 to 10, more preferably from 6 to 8 carbon atoms (examples of its substituent are V mentioned abovexe2x80x94this includes, for example, phenyl, 1-naphthyl, p-methoxyphenyl, p-methylphenyl, p-chlorophenyl), a substituted or unsubstituted heterocyclic group having from 1 to 20, preferably from 3 to 10, more preferably from 4 to 8 carbon atoms (examples of its substituent are V mentioned abovexe2x80x94this includes, for example, 2-furyl, 2-thienyl, 2-pyridyl, 3-pyrazolyl, 3-isoxazolyl, 3-isothiazolyl, 2-imidazolyl, 2-oxazolyl, 2-thiazolyl, 2-pyridazyl, 2-pyrimidiyl, 3-pyrazyl, 2-(1,3,5-triazolyl), 3-(1,2,4-triazolyl), 5-tetrazolyl, 5-methyl-2-thienyl, 4-methoxy-2-pyridyl).
R is preferably an unsubstituted alkyl group or a substituted alkyl group. The substituted alkyl group for it is preferably an alkyl group substituted with an acid group.
The acid group is described below. It is a group having a dissociating proton. Concretely, for example, it includes a sulfo group, a carboxyl group, a sulfato group, a group of xe2x80x94CHNHSO2xe2x80x94 (sulfonylcarbamoyl, carbonylsulfamoyl), a group of xe2x80x94CONHCOxe2x80x94 (carbonylcarbamoyl), a group of xe2x80x94SO2NHSO2xe2x80x94 (sulfonylsulfamoyl), a sulfonamido group, a sulfamoyl group, a phosphato group, a phosphono group, a boronic acid group, and a phenolic hydroxyl group, from which a proton is dissociated depending on its pKa and on the pH around it. Preferably, it is a proton-dissociating acid group capable of dissociating at least 90% proton dissociation at pH of from 5 to 11.
More preferably, it is a sulfo group, a carboxyl group, a group of xe2x80x94CHNHSO2xe2x80x94, a group of xe2x80x94CONHCOxe2x80x94, or a group of xe2x80x94SO2NHSO2xe2x80x94, even more preferably a sulfo group or a carboxyl group, and most preferably a sulfo group.
Concretely, preferred examples of the acid group-having alkyl group are 3-sulfopropyl, 4-sulfobutyl, 3-sulfobutyl, 2-sulfoethyl, carboxymethyl, carboxyethyl, carboxypropyl and methanesulfonylcarbamoylethyl; and most preferred are 3-sulfopropyl, 4-sulfobutyl, 3-sulfobutyl, 2-sulfoethyl, carboxymethyl and methanesulfonylcarbamoylethyl.
Preferred examples of the alkyl group substituted with any of a sulfo group, a carboxyl group, a group of xe2x80x94CHNHSO2xe2x80x94, a group of xe2x80x94CONHCOxe2x80x94, or a group of xe2x80x94SO2NHSO2xe2x80x94may be represented by the following formula:
Qa represents a linking group (preferably a divalent linking group) necessary for R to form an alkyl group; Ra, Rb, Rc and Rd each represent an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic-oxy group or an amino group.
Qa may be any and every linking group that satisfies the requirement as above, and is, for example, an atom or an atomic group that contains at least one of carbon, nitrogen, sulfur and oxygen atoms. Preferably, it is a linking group having from 0 to 10, more preferably from 1 to 5 carbon atoms of an alkylene group (e.g., methylene, ethylene, trimethylene, tetramethylene, pentamethylene, methyltrimethylene), an alkenylene group (e.g., ethenylone, propenylene), an alkynylene group (e.g. ethynylene, propenylene), anamido group, an ester group, asulfonamido group; a sulfonate group, an ureido group, a sulfonyl group, a sulfinyl group, a thioether group, an ether group, a carbonyl group or a group of xe2x80x94N(Vd)xe2x80x94 (in which Vd represents a hydrogen atom or a monovalent substituent, and the monovalent substituent may be any of V mentioned above) alone, or a combination of two or more of these groups.
The linking group may be further substituted with V mentioned above, and may have a ring (aromatic or non-aromatic hydrocarbon ring or hetero-ring).
More preferably, however, the linking group does not contain a hetero-atom. Also more preferably, the liking group is not substituted with a substituent of V mentioned above.
Even more preferably, the linking group is a divalent linking group having from 1 to 5 carbon atoms of an alkylene group having from 1 to 5 carbon atoms (e.g. , methylene, ethylene, trimethylene, tetramethylene, pentamethylene, methyltrimethylene), an alkenylene group having from 2 to 5 carbon atoms (e.g., ethenylene, propenylene) or an alkynylene group having from 2 to 5 carbon atoms (e.g., ethynylene, propynylene) alone, or a combination of two or more of these groups. Especially preferably, the linking group is an alkylene group having from 1 to 5 carbon atoms (more preferably, methylene, ethylene, trimethylene, tetramethylene).
In case where Xa is a sulfo group, Qa is more preferably ethylene, trimethylene, tetramethylene or methyltrimethylene, even more preferably trimethylene. In case where Xa is a carboxyl group, Qa is more preferably methylene, ethylene or trimethylene, even more preferably methylene.
In case where Xa is xe2x80x94CHNHSO2Ra, xe2x80x94SO2NHCORb, xe2x80x94CONHCORc or xe2x80x94SO2NHSO2Rd, Qa is more preferably methylene, ethylene or trimethylene, even more preferably methylene.
Ra, Rb, Rc and Rd each represent an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic-oxy group or an amino group. Preferably, these are any of the following groups.
Preferred examples of these groups are an unsubstituted alkyl group having from 1 to 18, preferably from 1 to 10, more preferably from 1 to 5 carbon atoms (e.g., methyl, ethyl, propyl, butyl), a substituted alkyl group having from 1 to 18, preferably from 1 to 10, more preferably from 1 to 5 carbon atoms (e.g., hydroxymethyl, trifluoromethyl, benzyl, carboxyethyl, ethoxycarbonylmethyl, acetylaminomethylxe2x80x94 the substituted alkyl group shall include an unsaturated hydrocarbon group having from 2 to 18, preferably from 3 to 10, more preferably from 3 to 5 carbon atoms (e.g., vinyl, ethynyl, 1-cyclohexenyl, benzylidyne, benzylidene)), a substituted or unsubstituted aryl group having from 6 to 20, preferably from 6 to 15, more preferably from 6 to 10 carbon atoms (e.g., phenyl, naphthyl, p-carboxyphenyl, p-nitrophenyl, 3,5-dichlorophenyl, p-cyanophenyl, m-fluorophenyl, p-tolyl), an optionally-substituted heterocyclic group having from 1 to 20, preferably from 2 to 10, more preferably from 4 to 6 carbon atoms (e.g., pyridyl, 5-methylpyridiyl, thienyl, furyl, morpholino, tetrahydrofurfuryl), an alkoxy group having from 1 to 10, preferably from 1 to 8 carbon atoms (e.g., methoxy, ethoxy, 2-methoxyethoxy, 2-hydroxyethoxy, 2-phenoxyethoxy), an aryloxy group having from 6 to 20, preferably from 6 to 12, more preferably from 6 to 10 carbon atoms (e.g., phenoxy, p-methylphenoxy, p-chlorophenoxy, naphthoxy), a heterocyclic-oxy group having from 1 to 20, preferably from 3 to 12, more preferably from 3 to 10 carbon atoms (this means an oxy group substituted with a heterocyclic group, including, for example, 2-thienyloxy, 2-morpholinoxy), and an amino group having from 0 to 20, preferably from 0 to 12, more preferably from 0 to 8 carbon atoms (e.g., amino, methylamino, dimethylamino, ethylamino, diethylamino, hydroxyethylamino, benzylamino, anilino, diphenylamino, cyclic morpholino, pyrrolidino). These may be further substituted with any of V mentioned above.
More preferably, they are any of methyl, ethyl and hydroxyethyl groups, and even more preferably they are methyl groups.
For its expression, the carboxyl group and the dissociating nitrogen atom of the acid group may be expressed as their non-dissociated forms, (CO2H) or (NH), or may also be expressed as their dissociated forms (CO2xe2x80x94) or (Nxe2x80x94). In fact, the acid group is either dissociated or non-dissociated, depending on the ambient condition such as pH in which the dye is kept.
In case where the acid group has a counter cation, it may be expressed, for example, as (CO2xe2x88x92, Na+) or (Nxe2x88x92, Na+). In its non-dissociated condition, the acid group is expressed as (CO2H) or (NH), but it may also be expressed as (CO2xe2x88x92, H+) or (Nxe2x88x92, H+) in which the proton serves as the counter cation.
V1, V2, V3 and V4 each independently represent a hydrogen atom or a monovalent substituent. The monovalent substituent for these is, for example, V mentioned above. Preferably, the monovalent substituent is more hydrophilic than iodine atom, more preferably its hydrophilicity is the same as or is higher than that of chlorine atom. Concretely, for example, the monovalent substituent is any of a bromine atom, a chlorine atom, a fluorine atom, a hydroxyl group, a carboxyl group, a methyl group, or a methoxy group.
Of V1, V2, V3 and V4, preferably, V3 and V4 are hydrogen atoms and V1 and V2 are hydrogen atoms or monovalent substituents; and more preferably, V1, V2, V3 and V4 are all hydrogen atoms.
M is in the formulae, and this indicates the presence of a cation or an anion that is needed for neutralizing the ionic charge of the dye (molecule). The matter as to whether a dye is cationic or anionic or has a net ionic charge depends on the substituents in the dye and on the ambient condition (e.g., pH) of the dye solution. Typical cations for M are inorganic cations such as hydrogen ion (H+), alkali metal ions (e.g., sodium ion, potassium ion, lithium ion), alkaline earth metal ions (e.g., calcium ion); and organic ions such as ammonium ions (e.g., ammonium ion, tetraalkylamnonium ion, triethylamonium ion, pyridinium ion, ethylpyridinium ion, 1,8-diazabicyclo[5.4.0]-7-undecenium ion). The anion may be either an inorganic anion or an organic anion, including, for example, halide anions (e.g., fluoride ion, chloride ion, bromide ion, iodide ion), substituted arylsulfonate ions (e.g., p-toluenesulfonate ion, p-chlorobenzenesulfonate ion), aryldisulfonate ions (e.g., 1,3-benzenedisulfonate ion, 1,5-naphthalenedisulfonate ion, 2,6-naphthalenedisulfonate ion), alkylsulfate ions (e.g., methylsulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, and trifluoromethanesulfonate ion. If desired, the dyes may be combined with ionic polymers or with any other reverse-charged dyes.
Preferably, the cation is any of sodium ion, potassium ion, triethylammonium ion, tetraethylammonium ion, pyridinium ion, ethylpyridinium ion, or methylpyridinium ion; more preferably, any of sodium, potassium, triethylammonium, pyridinium or N-ethylpyridinium ion. Also preferably, the anion is any of perchlorate ion, iodide ion, bromide ion, or substituted arylsulfonate ion (e.g., p-toluenesulfonate ion). Especially preferably, M is cation.
m indicates a number of 0 or more necessary for neutralizing the charge of the dye molecule. When the dye forms an internal salt, m is 0. Preferably, m is a number of from 0 to 4, more preferably 0, 1, 2 or 3.
D is a group necessary for forming the methine dye. Depending on D, any desired dye may be formed. Preferably, the dye is any of cyanine dye, merocyanine dye, rhodacyanine dye, trinuclear merocyanine dye, tetranuclear merocyanine dye, allopolar dye, helmicyanine dye, and styryl dye. The details of these dyes are described in, for example, F. M. Hamer""s Heterocyclic Compoundsxe2x80x94Cyanine Dyes and Related Compounds, John Wiley and Sons, New York, London, 1964; D. M. Sturmer""s Heterocyclic Compoundsxe2x80x94special Topics in Heterocyclic Chemistry, Chap. 18, Sci. 15, pp. 482-515, John Wiley and Sons, New York, London, 1977.
Preferred dyes for use in the present invention are those of formulae in columns 32-36 of U.S. Pat. No. 5,994,051; and those of formulae in columns 30-34 of U.S. Pat. No. 5,747,236. Also preferred for use herein are cyanine dyes, merocyanine dyes and rhodacyanine dyes of formulae (XI), (XII) and (XIII) in columns 21-22 of U.S. Pat. No. 5,340,694, in which, however, the numbers of n12, n15, n17 and n18 are not specifically defined and may be an integer of 0 or more, but is preferably at most 4.
For the methine dyes to be formed by D, more preferred are cyanine dyes and merocyanine dyes. When combined with the compound of formula (II), these dyes are more effective for improving the photographic properties of the silver halide photographic materials that contain them. More preferably, the methine dyes to be formed by D are cyanine dyes. When combined with the compound of formula (II), the cyanine dyes are even more effective for improving the photographic properties of the silver halide photographic materials that contain them.
Cyanine dyes of formulae (Ia), (Ib) and (Ic) with D therein may be expressed as the following resonance formulae. 
In formulae (Ia), (Ib) and (Ic), D is preferably D1 mentioned above, or any of Da, Db or Dc mentioned below. More preferably, D is D1 or Da. When combined with the compound of formula (II), the dyes of the preferred type are more effective for improving the photographic properties of the silver halide photographic materials that contain them. Most preferably, D1 is selected from D2 mentioned above. When combined with the compound of formula (II), the dyes of the most preferred type are still more effective for improving the photographic properties of the silver halide photographic materials that contain them. 
In Da, L81 and L82 each represent a methine group; n8 indicates 0, 1, 2, 3 or 4; Y81 represents an atomic group necessary for forming an acid nucleus or an acyclic acid terminal group. The atomic group may be condensed with any additional ring, or may be substituted with any other group. 
In Db, L91, L92, L93, L94, L95, L96 and L97 each represent a methine group; p9 indicates 0 or 1; n91 and n92 each indicate 0, 1, 2, 3 or 4; Y91 and Y92 each represent an atomic group necessary for forming a nitrogen-containing hetero-ring that may be condensed with any additional ring or may be substituted; R91 and R92 each represent a substituted or unsubstituted alkyl, aryl or heterocyclic group. 
In Dc, L101, L102, L103, L104, L105, L106 and L107 each represent a methine group; p10 indicates 0 or 1; n101 and n102 each indicate 0, 1, 2, 3 or 4; Y101 and Y102 each represent anatomic group necessary for forming a nitrogen-containing hetero-ring that may be condensed with any additional ring or may be substituted; R101 and R102 each represent a substituted or unsubstituted alkyl, aryl or heterocyclic group.
The nitrogen-containing hetero-ring represented by Z11, Y92 or Y102 is preferably a 5-membered or 6-membered nitrogen-containing hetero-ring, and this may be condensed with any additional ring (e.g., aromatic or non-aromatic carbon ring or hetero-ring, concretely V mentioned above). Preferably, the ring with which the hetero-ring represented by Z11, Y92 or Y102 is condensed is a 5-membered or 6-membered non-aromatic carbon ring or hetero-ring. More preferably, the carbon ring is a benzene ring or a naphthalene ring; and the hetero-ring is a furan ring or thiophene ring. Especially preferably, the ring to be condensed with the hetero-ring represented by Z11, Y92 or Y102 is a carbon ring, even more preferably a benzene ring.
Preferred examples of the nitrogen-containing hetero-ring with any of Z11, Y92 or Y102 are thiazoline ring, thiazole ring, benzothiazole ring, oxazoline ring, oxazole ring, benzoxazole ring, selenazoline ring, selenazole ring, benzoselenazole ring, tellurazoline ring, tellurazole ring, benzotellurazole ring, 3,3-dialkylindolenine ring (e.g., 3,3-dimethylindolenine), imidazoline ring, imidazole ring, benzimidazole ring, isoxazole ring, isothiazole ring, pyrazole ring, 2-pyridine ring, 4-pyridine ring, 2-quinoline ring, 4-quinoline ring, 1-isoquinoline ring, 3-isoquinoline ring, isidazo[4,5-b]quinoxaline ring, oxadiazole ring, thiadiazole ring, tetrazole ring, pyrimidine ring, and these rings condensed with benzene ring.
More preferably, the hetero-ring is any of benzoxazole ring, benzothiazole ring, benzimidazole ring or quinoline ring; even more preferably benzoxazole ring or benzothiazole ring. These rings may be substituted with any of V mentioned above. Concretely, examples of Z11, Z12, Z13, Z14 and Z16 described in columns 23-24 of U.S. Pat. No. 5,340,694 are referred to for specific examples of the rings.
Y81 is an atomic group necessary for forming an acyclic or cyclic acid nucleus, and it may form any and every acid nucleus generally in ordinary merocyanine dyes. In one preferred form of the acid nucleus, a thiocarbonyl group or a carbonyl group is adjacent to the methine chain-bonding site of Y81.
The acid nucleus referred to herein is defined, for example, as in T. H. James"" The Theory of the Photographic Process, 4th Ed., MacMillan Publishing, 1977, p. 198. Concretely, it is described in, for example, U.S. Pat. Nos. 3,567,719, 3,575,869, 3,804,634, 3,837,862, 4,002,480, 4,925,777, and JP-A 3-167546.
Preferably, the acid nucleus is a 5- or 6-membered nitrogen-containing hetero-ring with any of carbon, nitrogen and chalcogen (typically, oxygen, sulfur, selenium and tellurium) atoms. For example, it includes the following:
2-Pyrazolin-5-one, pyrazolidine-3,5-dione, imidazolin-5-one, hydantoin, 2 or 4-thiohydantoin, 2-iminoxazolidin-4-one, 2-oxazolin-5-one, 2-thioxazoline-2,4-dione, isoxazolin-5-one, 2-thiazolin-4-one, thiazolidin-4-one, thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, isorhodanine, indane-1,3-dione, thiophen-3-one, thiophen-3-one-1,1-dioxide, indolin-2-one, indolin-3-one, 2-oxoindazolinium, 3-oxoindazolinium, 5,7-dioxo-6,7-dihydrothiazolo [3,2-a]pyrinlidine, cyclohexane-1,3-dione, 3,4-dihydroisoquinolin-4-one, 1,3-dioxane-4,6-dione, barbituric acid, 2-thiobarbituric acid, chromane-2,4-dione, indazolin-2-one, pyridol[1,2-a]pyrimidine-1,3-dione, pyrazolo[1,5-b]quinazolone, pyrazolo[1,5-a]benzimidazole, pyrazolopyridone, 1,2,3,4-tetrahydroquinoline-2,4-dione, 3-oxo-2,3-dihydrobenzo[d]thiopnene-1,1-dioxide, and 3-dicyanomethylene-2,3-dihydrobenzo[d]thiophene-1,1-dioxide nuclei; exomethylene-structured nuclei derived from these nuclei by substituting the carbonyl or thiocarbonyl group in these with an active methylone moiety of ketomethylene or cyanomethylene-structured active methylene compounds; and nuclei of their repetitions.
Preferably, Y81 is hydantoin, 2 or 4-thiohydantoin, 2-oxazolin-5-one, 2-thioxazoline-2,4-dione, thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, barbituric acid or 2-thiobarbituric acid, more preferably hydantoin, 2 or 4-thiohydantoin, 2-oxazolin-5-one, rhodanine, barbituric acid or 2-thiobarbituric acid. Even more preferably, it is 2 or 4-thiohydantoin, 2-oxazoline-5-one or rhodanine, and most preferably rhodanine.
The nitrogen-containing hetero-ring to be formed with Y91 or Y101 is preferably 5- or 6-membered, and more preferably it is derived from the hetero-ring of Y91 by removing the oxo or thioxo group from it. Even sore preferably, it is derived from hydantoin, 2 or 4-thiohydantoin, 2-oxazolin-5-one, 5-thioxazoline-2,4-dione, thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dione, barbituric acid or 2-thiobarbituric acid by removing the oxo or thioxo group. Even more preferably, it is derived from hydantoin, 2 or 4-thiohydantoin, 2-oxazlin-5-one, rhodanine, barbituric acid or 2-thiobarbituric acid by removing the oxo or thioxo group; still more preferably, it is derived from 2 or 4-thiohydantoin, 2-oxazolin-5-one or rhodanine by removing the oxo or thioxo group; and most preferably, it is derived from rhodanine by removing the thioxo group.
R12, R22, R91, R92, R101, R102, and the substituent (if any, it is represented by R81) on the nitrogen atom of the acid nucleus Y81 each are a substituted or unsubstituted alkyl, aryl or heterocyclic group, for which preferred are those mentioned hereinabove for R in the methine dyes of formulae (Ia), (Ib) and (Ic).
More preferably, R12, R22, R81, R91, R92, R101 and R102 each are a substituted or unsubstituted alkyl group, and even more preferably an alkyl group substituted with an acid group. Concretely, for the acid group-substituted alkyl group for these, referred to are those mentioned hereinabove for R; and the preferred examples of the group for these may be the same as those mentioned hereinabove for R.
L11, L12, L13, L14, L15, L21, L22, L23, L81, L82, L91, L92, L93, L94, L95, L96, L97, L101, L102, L103, L104, L105, L106 and L107 each independently represent a methine group. The methine group for these may be optionally substituted, for which referred to are the substituents V mentioned above.
It may form a ring along with any other methine group, or may form a ring along with any of Z11, Y81, Y91, Y92, Y101, Y102, R, R12, R22, R91, R92, R101 or R102.
Preferably, L14, L15, L96, L97, L106 and L107 are unsubstituted methine groups.
n1, n2, n8, n91, n92, n101 and n102 each indicate 0, 1, 2, 3 or 4. When they are 2 or more, the dyes have multiple methine groups in one molecule, in which however, the multiple methine groups may not be the same. Preferably, n1, n2, n8, n91 and n102 each are 0, 1, 2 or 3, more preferably 0, 1 or 2, even more preferably 0 or 1. Also preferably, n92 and n101 each are 0 or 1, and more preferably they are both 0.
In case where n1 is 0, L11 is preferably an unsubstituted methine group; and in case where n1 is 1, L12 is preferably a methine group substituted with an unsubstituted alkyl group, and L11 and L13 are both unsubstituted methine groups. More preferably, L12 is a methyl-substituted methine group or an ethyl-substituted methine group, even more preferably an ethyl-substituted methine group.
In case where n2 is 0, L21 is preferably an unsubstituted methine group; and in case where n2 is 1, L22 is preferably a methine group substituted with an unsubstituted alkyl group, and L21 and L23 are both unsubstituted methine groups. More preferably, L22 is a methyl-substituted methine group or an ethyl-substituted methine group, even more preferably an ethyl-substituted methine group.
p1, p9 and p10 each independently indicate 0 or 1, but preferably they are 0.
X22 represents a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a nitrogen atom (Nxe2x80x94Ve), or a carbon atom (CVfVg). Ve, Vf and Vg each represent a hydrogen atom, or a substituent (e.g., V mentioned above), and are preferably any of a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. For the alkyl group, the aryl group and the heterocyclic group for these, referred to are those mentioned hereinabove for R. For these, preferred are the same groups as those for R. More preferably, these Ve, Vf and Vg are alkyl groups.
Preferably, X22 is a sulfur, oxygen, selenium or nitrogen atom, more preferably a sulfur, oxygen or selenium atom, even more preferably a sulfur or oxygen atom, most preferably a sulfur
In case where D is D1 or D2 in formulae (Ia), (Ib) and (Ic), it is desirable that R and R12, or R and R22 are both acid group-substituted alkyl groups. Regarding the combination of R and R12, and that of R and R22, it is desirable that any one of Rand R12, and any one of R and R22 are sulfo group-substituted alkyl groups, and the others each are an alkyl group substituted with an acid group except sulfo group.
For the sulfo group-substituted alkyl group, and the alkyl group substituted with an acid group except sulfo group, referred to are those mentioned hereinabove for R. For these, preferred are the same as those mentioned hereinabove for R.
More preferably, the sulfo group-having alkyl group is a 3-sulfopropyl, 4-sulfobutyl, 3-sulfobutyl or 2-sulfoethyl group, even more preferably a 2-sulfopropyl group. The alkyl group having an acid group except sulfo group is, for example, a carboxymethyl or methanesulfonylcarbamoylmethyl group.
V21, V22, V23 and V24 each represent a hydrogen atom or a substituent. For the substituent for these, referred to are those mentioned hereinabove for V. However, two adjacent substituents do not bond to each other to form a saturated or unsaturated condensed ring. Preferably, the substituent for these is not an aryl or aromatic heterocyclic group. Preferably, V21 and V24 are hydrogen atoms; and V22 and V23 each are a hydrogen atom, or an alkyl group (e.g., methyl), an alkoxy group (e.g., methoxy), an alkylthio group (e.g., methylthio), a cyano group, or a halogen atom (e.g., fluorine, chlorine, bromine, iodine). More preferably, V23 is a hydrogen atom, and V22 is an alkyl group, an alkoxy group or a halogen atom. Even more preferably, V22 is a halogen atom, still more preferably a chlorine or bromine atom, most preferably a chlorine atom. The preferred embodiments produce better results.
When the dye of formula (Ia) (Ib) or (Ic) is combined with the compound of formula (II) in the present invention, they are preferably so combined that their spectral sensitivity peak wavelength is not longer than 100 nm, more preferably not longer than 70 nm, even more preferably not longer than 50 nm, still more preferably not longer than 40 nm.
Preferred combinations of the cyanine dye of formula (Ia), (Ib) or (Ic) and the compound of formula (II) are discussed in point of the structural viewpoint of the compounds. Preferably, the cyanine dye of formula (Ia), (Ib) or (Ic) having three methine chains is combined with the compound of formula (II) also having three methine chains; and the cyanine dye of formula (Ia), (Ib) or (Ic) having one methine chain is preferably combined with the compound of formula(II) also having one methine chain. When the dye of formula (Ia), (Ib) or (Ic) is combined with the compound of formula (II) all having three methine chains and when the dye of formula (Ia), (Ib) or (Ic) has a benzothiazole nucleus and a benzoxazole nucleus, then it is desirable that the compound of formula (II) has two benzothiazole nuclei; but when the dye of formula (Ia), (Ib) or (Ic) has two benzoxazole nuclei, then it is desirable that the compound of formula (II) has two benzoxazole nuclei. When the dye of formula (Ia), (Ib) or (Ic) and the compound of formula (II) all have one methine chain and when the dye of formula (Ia), (Ib) or (Ic) has two benzothiazole nuclei, then it is desirable that the compound of formula (II) has two benzothiazole nuclei.
Next described in detail is the cyanine dye of formula (II) to be combined with the methine dye of formulae (Ia), (Ib) and (Ic).
In formula (II), the nitrogen-containing hetero-ring with any of Z31 and Z32 is preferably 5-membered or 6-membered, and it may be condensed with any other ring (e.g., aromatic or non-aromatic carbon ring or hetero-ring, concretely, V mentioned above). The ring with which the hetero-ring with Z31 or Z32 is condensed is preferably a 5-membered or 6-membered aromatic carbon ring, more preferably a benzene or naphthalene ring, even more preferably a benzene ring.
The compound of formula (II) does not include the compounds of formulae (Ia), (Ib) and (Ic). In formula (IIxe2x80x2 the nitrogen-containing hetero-ring with any of Z31 and Z32 is not condensed with any other ring such as dioxolane ring, different from that in formula (Ia), (Ib) or (Ic). In formula (II), the other hetero-rings may be condensed with any additional ring, but preferably they are not.
Preferably, Z31 and Z32 are any of thiazoline ring, thiazole ring, benzothiazole ring, oxazoline ring, oxazole ring, benzoxazole ring, selenazoline ring, selenazole ring, benzoselenazole ring, tellurazoline ring, tellurazole ring, benzotellurazole ring, 3,3-dialkylindolenine ring (e.g., 3,3-dimethylindolenine), imidazoline ring, imidazole ring, benzimidazole ring, isoxazole ring, isothiazole ring, pyrazole ring, 2-pyridine ring, 4-pyridine ring, 2-quinoline ring, 4-quinoline ring, 1-isoquinoline ring, 3-isoquinoline ring, imidazo[4,5-b]quinoxaline ring, oxadiazole ring, thiadiazole ring, tetrazole ring, pyriraidine ring; and these rings condensed with any carbon ring such as benzene ring or naphthalene ring.
More preferably, they are benzoxazole ring, benzothiazole ring, benzimidazole ring and quinoline ring; even more preferably benzoxazole ring or benzothiazole ring. These may be substituted with any substituent of V mentioned above. Concretely referred to for their examples are the examples of Z11, Z12, Z13, Z14 and Z16 mentioned in columns 23-24 of U.S. Pat. No. 5,340,694.
For the alkyl, aryl and heterocyclic groups for R31 and R32, referred to are those mentioned hereinabove for R. Preferably, R31 and R32 each are a substituted or unsubstituted alkyl group. More preferably at least one of them is an alkyl group substituted with an acid group. More preferably, R31 and R32 are both acid group-substituted alkyl groups. For preferred examples of the acid group-substituted alkyl group for R31 and R32, concretely referred to are those mentioned hereinabove as preferred examples for R.
Regarding the combination of R31 and R32, it is desirable that any one of R31 and R32 is a sulfo group-substituted alkyl group and the other one is an alkyl group substituted with an acid group except sulfo group, like the combination of R and R12 and the combination of R and R22 in formulae (Ia), (Ib) and (Ic) where D is D1 or D2.
For the preferred examples of the sulfo group-substituted alkyl group and the alkyl group substituted with an acid group except sulfo group, referred to are the same as those mentioned hereinabove for R.
More preferably, the sulfo group-having alkyl group is a 3-sulfopropyl, 4-sulfobutyl, 3-sulfobutyl or 2-sulfoethyl group, even more preferably a 3-sulfopropyl group. Also preferably, the alkyl group substituted with any acid group except sulfo group is a carboxymethyl or methanesulfonylcarbamoylmethyl group.
The methine group for L31, L32, L33, L34, L35, L36 and L37 may be substituted or unsubstituted. For the substituent for the group, referred to are those of V mentioned above.
Preferably, L31, L32, L36 and L37 are unsubstituted methine groups.
n3 indicates 0, 1, 2, 3 or 4. When n3 is 2 or more, the dye of formula (II) has multiple methine groups in one molecule, in which, however, the multiple methine groups may not be the same. Preferably, n3 is 0, 1, 2 or 3, more preferably 0, 1 or 2, even more preferably 0 or 1.
In case where n3 is 0, L33 is preferably an unsubstituted methine group; and in case where n3 is 1, L34 is preferably a methine group substituted with an unsubstituted alkyl group, and L33 and L35 are both unsubstituted methine groups. More preferably, L34 is a methyl-substituted methine group or an ethyl-substituted methine group, even more preferably an ethyl-substituted methine group.
p31 and p32 each indicate 0 or 1, but preferably they are 0.
M3 is an ion mentioned hereinabove for M, and is preferably a cation. More preferably, the cation for M3 is sodium, potassium, triethylammonium, pyridinium or N-ethylpyridinium.
m3 indicates a number of 0 or more necessary for neutralizing the charge of the molecule, and it is 0 when the compound of formula (II) forma an internal salt. Preferably, it is 0, 1, 2 or 3.
Preferably, the methine dye of formula (II) is represented by formula (IIa) mentioned above.
In formula (IIa), X41 and X42 each represent a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a nitrogen atom (Nxe2x80x94Vh), or a carbon atom (CViVj). Vh, Vi and Vj each represent a hydrogen atom, or a substituent (e.g., V mentioned above), but are preferably any of a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. For the alkyl group, the aryl group and the heterocyclic group for these, referred to are those mentioned hereinunder for R. For these, preferred are the same groups as those for R. More preferably, these Vh, Vi and Vj are alkyl groups.
Preferably, X41 and X42 each are a sulfur, oxygen, selenium or nitrogen atom, more preferably a sulfur, oxygen or selenium atom, even more preferably a sulfur or oxygen atom, most preferably a sulfur atom.
The alkyl, aryl and heterocyclic groups for R41 and R42, referred to are those mentioned hereinabove for R. Preferably, R41 and R42 are the same as R31 and R32 in formula (II), or are in the same combination as that of R31 and R32 in formula (II).
For the substituent for V41, V42, V43, V44, V45, V46, V47 and V48, referred to are those of V mentioned above, and the two adjacent substituents may bond to each other to form a saturated or unsaturated condensed ring. Preferably, the condensed ring is with a carbon ring. Examples of the saturated or unsaturated carbon ring are benzene ring, cyclohexene ring and naphthalene ring. Preferably, however, the groups do not form a condensed ring.
Preferably, V41, V42, V45 and V48 are hydrogen atoms; V42, V43, V46 and V47 each are a hydrogen atom, an alkyl group (e.g., methyl), an aryl group (e.g., phenyl), an aromatic heterocyclic group (e.g., 1-pyrrolyl), an alkoxy group (e.g., methoxy), an alkylthio group (e.g., methylthio), a cyano group or a halogen atom (e.g., fluorine, chlorine, bromine, iodine). More preferably, V43 and V47 are hydrogen atoms; and V42 and V46 are halogen atoms (even more preferably, chlorine or bromine), still more preferably chlorine atoms.
The methine group for L41, L42 and L43 may be unsubstituted or substituted. For the substituent for the group, referred to are those of V mentioned above.
n4 indicates 0, 1, 2, 3 or 4. When n4 is 2 or more, the compound has multiple methine groups in one molecule, in which, however, the multiple methine groups may not be the same. Preferably, n4 is 0, 1, 2 or 3, more preferably 0, 1 or 2, even more preferably 0 or 1.
In case whore n4 is 0, L41 is preferably an unsubstituted methine group; and in case where n4 is 1, L42 is preferably a methine group substituted with an unsubstituted alkyl group, and L41 and L43 are both unsubstituted methine groups. More preferably, L42 is a methyl-substituted methine group or an ethyl-substituted methine group, even more preferably an ethyl-substituted methine group.
For M4, referred to are the ions mentioned hereinabove for M. Especially preferably, M4 is a cation. Preferred examples of the cation are sodium, potassium, triethylamfonium, pyridinium, and N-ethylpyridinium.
m4 indicates a number of 0 or more necessary for neutralizing the charge of the molecule. In case where the dye forms an internal salt, m4 is 0. Preferably, m4 is 0, 1, 2 or 3.
The methine dye of formula (IIa) is more preferably represented by formula (III) mentioned above in case where it is used in green-sensitive to red-sensitive emulsions, or by formula (IV) also mentioned above in case where it is used in blue-sensitive emulsions.
The dyes of formula (III) are described in detail hereinunder.
In formula (III), X51 and X52 each represent an oxygen or sulfur atom. When the dye of formula (III) is in a green-sensitive emulsion, X51 is preferably an oxygen or sulfur atom, and X52 is preferably an oxygen atom; and more preferably X51 and X52 are both oxygen atoms. When the dye is in a red-sensitive emulsion, X51 is preferably an oxygen or sulfur atom, and X52 is preferably a sulfur atom; but more preferably X51 and X52 are both sulfur atoms.
For the alkyl, aryl and heterocyclic groups for R51, R52 and R53, referred to are those mentioned hereinabove for R. Preferably, R51 and R52 are the same as those of R31 and R32 in formula (II), and their combination is also preferably the same as the combination of R31 and R32 in formula (II).
Also preferably, R53 is an unsubstituted alkyl group, more preferably a methyl or ethyl group.
For the substituent for V51, V52, V53, V54, V55 and V56, referred to are those of V mentioned above, but the two adjacent substituents of these V51, V52, V53, V54, V55 and V56 do not bond to each other to form a saturated or unsaturated condensed ring. Preferably, V51, V53, V54 and V56 are hydrogen atoms; V52 and V55 each are an alkyl group (e.g., methyl), an aryl group (e.g., phenyl), an aromatic heterocyclic group (e.g., 1-pyrrolyl), an alkoxy group (e.g., methoxy), an alkylthio group (e.g., methylthio), a cyano group or a halogen atom (e.g., fluorine, chlorine, bromine, iodine). More preferably, V52 and V55 each are a halogen atom, even more preferably a chlorine or bromine atom, and most preferably they are both chlorine atoms.
For M5, referred to are the ions mentioned hereinabove for M. Preferably, M5 is a cation. Preferred examples of the cation for it are sodium, potassium, triethylammonium, pyridinium and N-ethylpyridinium.
m5 indicates a number of 0 or more necessary for neutralizing the charge of the molecule. When the dye forms a internal salt, m5 is 0. Preferably, m5 is 0, 1, 2 or 3.
The dyes of formula (IV) are described in detail hereinunder.
In formula (IV), X61 represents an oxygen or sulfur atom, and is preferably a sulfur atom.
For the alkyl, aryl and heterocyclic groups for R61 and R62, referred to are those mentioned hereinabove for R. Preferably, R61 and R62 are the same as those of R31 and R32 in formula (II), and their combination is also preferably the same as the combination of R31 and R32 in formula (II).
For the substituent for V61, V62, V63, V64, V65 and V66, referred to are those of V mentioned above, but the two adjacent substituents of these V61, V62, V63, V64, V65 and V66 do not bond to each other to form a saturated or unsaturated condensed ring. Preferably, V61, V63, V64 and V66 are hydrogen atoms; V62 and V65 each are an alkyl group (e.g., methyl), an aryl group (e.g., phenyl), an aromatic heterocyclic group (e.g., 1-pyrrolyl), an alkoxy group (e.g., methoxy), an alkylthio group (e.g., methylthio), a cyano group or a halogen atom (e.g., fluorine, chlorine, bromine, iodine). More preferably, V62 and V65 each are a halogen atom, even more preferably a chlorine or bromine atom, and most preferably they are both chlorine atoms.
For M6, referred to are the ions mentioned hereinabove for M. Preferably, M6 is a cation. Preferred examples of the cation for it are sodium, potassium, triethylammonium, pyridinium and N-ethylpyridinium.
m6 indicates a number of 0 or more necessary for neutralizing the charge of the molecule. When the dye forms an internal salt, m6 is 0. Preferably, m6 is 0, 1, 2 or 3.
To be in the silver halide emulsion in the present invention, preferred combinations of the compound of formula (Ia), (Ib) or (Ic) and the compound of formula (II) are mentioned below.
In a red-sensitive emulsion layer, the compound of formula (II) is preferably one of formula (III) in which X51 and X52 are both sulfur atoms; R51 and R52 each are a sulfoalkyl group, a carboxyalkyl group or an alkylsulfonylcarbamoylalkyl group; R53 is a methyl or ethyl group; V51, V53, V54 and V56 are all hydrogen atoms; V52 and V55 each are an alkyl group (e.g., methyl), an alkoxy group (e.g., methoxy), an alkylthio group (e.g., methylthio), a cyano group or a halogen atom (e.g., fluorine, chlorine, bromine, iodine), more preferably a halogen atom, and even more preferably they are both chlorine atoms; M5 is an organic or inorganic monovalent cation; and m5 is 0 or 1.
The compound of formula (Ia), (Ib) or (Ic) to be combined with the compound of that formula (III) is preferably any one of formula (Ia) or (Ib) in which D is D2; one of Z1 and X22 is an oxygen atom and the other is a sulfur atom; V1, V2, V3 and V4 are all hydrogen atoms; R and R22 each are a sulfoalkyl group, a carboxyalkyl group or an alkylsulfonylcarbamoylalkyl group; n2 is 1; L21 and L23 are both unsubstituted methine groups; L22 is a methyl-substituted methine group or an ethyl-substituted methine group; V21, V23 and V24 are hydrogen atoms; V22 is an alkyl group (e.g., methyl), an alkoxy group (e.g., methoxy), an alkylthio group (e.g., methylthio), a cyano group or a halogen atom (e.g., fluorine, chlorine, bromine, iodine), more preferably a halogen atom; M is an organic or inorganic monovalent cation; and m is 0 or 1.
In a green-sensitive emulsion layer, the compound of formula (II) is preferably one of formula (III) in which X51 and X52 are both oxygen atoms; R51 and R52 each are a sulfoalkyl group, a carboxyalkyl group or an alkylsulfonylcarbamoylalkyl group; R53 is a methyl or ethyl group; V51, V53, ,V54 and V56 are all hydrogen atoms; V52 and V55 each are an alkyl group (e.g., methyl), an aryl group (e.g., phenyl), an aromatic heterocyclic group (e.g., 2-thienyl), an alkoxy group (e.g., methoxy), an alkylthio group (e.g., methylthic), a cyano group or a halogen atom (e.g., fluorine, chlorine, bromine, iodine), more preferably a halogen atom; M5 is an organic or inorganic monovalent cation; and m5 is 0 or 1.
The compound of formula (Ia), (Ib) or (Ic) to be combined with the compound of that formula (III) is preferably any one of formula (Ia) or (Ib) in which D is D2; one of Z1 and X22 is an oxygen atom and the other is a sulfur atom, or both of these are oxygen atoms, more preferably Z1 and X22 are both oxygen atoms; V1, V2, V3 and V4 are all hydrogen atoms; R and R22 each are a sulfoalkyl group, a carboxyalkyl group or an alkylsulfonylcarbamoylalkyl group; n2 is 1; L21 and L23 are both unsubstituted methine groups; L22 is a methyl-substituted methine group or an ethyl-substituted methine group; V21, V23 and V24 are hydrogen atoms; V22 is an alkyl group (e.g., methyl), an aryl group (e.g., phenyl), an aromatic heterocyclic group (e.g., 2-thienyl), an alkoxy group (e.g.,methoxy), an alkylthio group (e.g., methylthio), a cyano group or a halogen atom (e.g., fluorine, chlorine, bromine, iodine), more preferably a halogen atom; M is an organic or inorganic monovalent cation; and m is 0 or 1.
In a blue-sensitive emulsion layer, the compound of formula (II) is preferably one of formula (IV) in which X61 is an oxygen atom; R61 and R62 each are a sulfoalkyl group, a carboxyalkyl group or an alkylsulfonylcarbamoylalkyl group; V61, V63, V64 and V66 are all hydrogen atoms; V62 and V65 each are an alkyl group (e.g., methyl), an aryl group (e.g., phenyl), an aromatic heterocyclic group (e.g., 1-pyrrolyl), an alkoxy group (e.g., methoxy), an alkylthio group (e.g., methylthio), a cyano group or a halogen atom (e.g., fluorine, chlorine, bromine, iodine), more preferably a halogen atom, even more preferably they are both chlorine atoms; M6 is an organic or inorganic monovalent cation; and m6 is 0 or 1.
The compound of formula (Ia), (Ib) or (Ic) to be combined with the compound of that formula (IV) is preferably any one of formula (Ia) or (Ib) in which D is D2; Z1 and X22 are both sulfur atoms; V1, V2, V3 and V4 are all hydrogen atoms; R and R22 each are a sulfoalkyl group, a carboxyalkyl group or an alkylsulfonylcarbamoylalkyl group; n2 is 0; L21 is an unsubstituted methine group; V21, V23 and V24 are hydrogen atoms; V22 is an alkyl group (e.g., methyl), an alkoxy group (e.g., methoxy), an alkylthio group (e.g., methylthio), a cyano group or a halogen atom (e.g., fluorine, chlorine, bromine, iodine), more preferably a halogen atom, even more preferably a chlorine or bromine atom; M is an organic or inorganic monovalent cation; and m is 0 or 1.
Specific examples of the compounds of formula (Ia), (Ib) and (Ic) for use in the present invention (including those of a more specific concept) are shown below, which, however, are not intended to restrict the scope of the present invention. 
Specific examples of the compounds of formula (II) for use in the invention (including those of a more specific concept, compounds of formula (IIa), compounds of formula (III) and compounds of formula (IV)) are shown below, which, however, are not intended to restrict the scope of the present invention. 
The compounds of formulae (Ia), (Ib), (Ic) and (II) for use in the present invention (including those of a more specific concept) are produced, for example, according to the methods described in F. M. Hamer""s, Heterocyclic Compoundsxe2x80x94Cyanine Dyes and Related Compounds, John Wiley and Sons, New York, London, 1964; D. M. Sturmer""s, Heterocyclic Compoundsxe2x80x94Special Topics in Heterocyclic Chemistry, Chap. 18, Sec. 14, pp. 482-515, John Wiley and Sons, New York, London, 1977; and Rodd""s Chemistry of Carbon Compound, 2nd Ed., Vol. IV, Part B, 1977, Chap. 15, pp. 369-422, Elsevier Science Publishing Company, Inc., New York.
Regarding the combination of the compound of formula (Ia), (Ib) or (Ic) and the compound of formula (II) to be in the photosensitive emulsion in the present invention, one or more different types of the former compounds may be combined with one or more different types of the latter compounds in one and the same emulsion.
The ratio of the compound of formula (Ia), (Ib) or (Ic) to the compound of formula (II) to be in one and the same emulsion in the present invention is not specifically defined and may be determined in any desired manner, depending on the use and the object of the photographic material of the present invention. Preferably, the ratio falls between 1000/1 and 1/1000, more preferably between 100/1 and 1/100, further more preferably between 10/1 and 1/10, still more preferably between 5/1 and 1/5.
The compound of formula (Ia), (Ib) or (Ic) and the compound of formula (II) may be combined with any other sensitizing dye in one and the same emulsion. Preferred examples of the additional dyes that may be combined with the specific sensitizing dyes in the present invention are cyanine dyes, merocyanine dyes, rhodacyanine dyes, trinuclear merocyanine dyes, tetranuclear merocyonine dyes, allopolar dyes, hemicyanine eyes and styryl dyes. More preferred are cyanine dyes, merocyanine dyes and rhodacyanine dyes; and even more preferred are cyanine dyes. The details of these dyes are described, for example, in F. M. Hamer""s, Heterocyclic Compoundsxe2x80x94Cyanine Dyes and Related Compounds, John Wiley and Sons, New York, London, 1964; D. M. Sturmer""s, Heterocyclic Compoundsxe2x80x94Special Topics in Heterocyclic Chemistry, Chap. 18, Sec. 14, pp. 482-515, John Wiley and Sons, New York, London, 1977.
For further information, the dyes described in RD 17643, pp. 23-24; RD 18716, from page 648, right column to page 649, right column; RD 308119, from page 996, right column to page 998, right column; EP 0565096A1, p.65, lines 7-10 are preferred for use in the present invention. In addition, also preferred are the sensitizing dyes described and exemplified as their general formulae and concrete examples in U.S. Pat. No. 5,747,236 (especially, pp. 30-39) and in U.S. Pat. No. 5,340,694 (especially, pp. 21-60; sensitizing dyes of general formulae (XI), (XII) and (XIII) in which the numbers of n12, n15, n17 and n18 are not defined and may be integers of 0 or more, but preferably at most 4).
One or more of these additional sensitizing dyes may be used herein. In case where two or more such additional sensitizing dyes are used, those effective for supersensitization are preferred. Their typical examples are described, for example, in U.S. Pat. Nos. 2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641, 3,617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,303,377, 3,769,301, 3,814,609, 3,837,862, 4,026,707; BP 1,344,281, 1,507,803; JP-B 43-49336 (The term xe2x80x9cJP-Bxe2x80x9d as used herein means an examined Japanese Patent Publicationxe2x80x9d), JP-B 53-12375, JP-A 52-110618, and JP-A 52-109925.
Dyes not having the capability of spectral sensitization by themselves or substances not substantially absorbing visible light, but those having the capability of supersensitization maybe contained in the emulsion along with the sensitizing dyes.
Supersonsitizers useful for spectral sensitization in the present invention (e.g., pyrimidylamino compounds, triazinylamino compounds, azolium compounds, aminostyryl compounds, aromatic organic acid-formaldehyde condensates, azaindene compounds, cadmium salts), and the combination of supersensitizers and sensitizing dyes are described in, for example, U.S. Pat. Nos. 3,511,664, 3,615,613, 3,615,632, 3,615,641, 4,596,767, 4,945,038, 4,965,182, 4,965,182, 2,933,390, 3,635,721, 3,743,510, 3,617,295, 3,635,721. Regarding the method of using them, preferably referred to are the disclosures in these patent specifications.
The silver halide photographic emulsion and the silver halide photographic material of the present invention are described in detail hereinunder.
The methine dyes of formulae (Ia), (Ib) and (Ic) and those of formula (II) for use in the present invention serve as sensitizing dyes. These methine dyes (and also any other additional sensitizing dyes and supersensitizers) may be added to silver halide emulsions in any stage heretofore considered good in the art of emulsion preparation. For example, as in U.S. Pat. Nos. 2,735,766, 3,628,960, 4,183,756, 4,225,666; JP-A58-184142, JP-A 60-196749, they may be added to the emulsions in any stage of silver halide grain formation and/or before desalting, during desalting and/or after desalting but before the start of chemical ripening; or as in JP-A 58-113920, in any stage just before chemical ripening or during chemical ripening, or after chemical ripening but before emulsion coating. As in U.S. Pat. No. 4,225,666 and JP-A 58-7629, one compounder two or more compounds having foreign structures may be added to emulsions in two or more divided portions, for example, during silver halide grain formation and chemical ripening, or after chemical ripening, or before, during or after chemical ripening. In case where the compounds are added in such divided portions, the type of the compound to be added singly may be varied and the combination of the compounds to be added together may also be varied.
The amount of the methine dyes to be added to the emulsions may be varied in any desired manner, depending on the shape and the size of the silver halide grains in the emulsions (the same shall apply also to other sensitizing dyes and supersensitizers). Preferably, for example, it may be from 1xc3x9710xe2x88x928 mols to 8xc3x9710xe2x88x921 mols, more preferably from 1xc3x9710xe2x88x926 to 8xc3x9710xe2x88x923 mols, per mol of the silver halide. For example, when the grain size of the silver halide grains to be sensitized is from 0.2 to 1.3 xcexcm, the amount of the sensitizing dye to be added to the grains is preferably from 2xc3x9710xe2x88x926 to 3.5xc3x9710xe2x88x923 mols, more preferably from 7.5xc3x9710xe2x88x926 to 1.5xc3x9710xe2x88x923 mols.
In the present invention, the methine dyes may be directly dispersed in emulsions (the same shall apply also to other sensitizing dyes and supersensitizers). Alternatively, they maybe first dissolved in a suitable solvent such as methylalcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine or a mixed solvent of these, and the resulting solution may be added to emulsions. In this case, additives such as base, acid and surfactant maybe in the solution. If desired, ultrasonic waves may be used for dissolving the dyes. For adding the compounds to emulsions, for example, employable area method of dissolving the compounds in a volatile organic solvent, dispersing the resulting solution in a hydrophilic colloid, and adding the resulting dispersion to emulsions, as in U.S. Pat. No. 3,469,987; a method of dispersing the compounds in a water-soluble solvent, and adding the resulting dispersion to emulsions, as in JP-B 46-24185; a method of dissolving the compounds in a surfactant, and adding the resulting solution to emulsions, as in U.S. Pat. No. 3,822,135; a method of dissolving the compounds along with a red-shift compound and adding the resulting solution to emulsions, as in JP-A 51-74624; and a method of dissolving the compounds in an acid not substantially containing water, and adding the resulting solution to emulsions, as in JP-A 50-80826. In addition, other methods such as those described in U.S. Pat. Nos. 2,912,343, 3,342,605, 2,996,287, 3,429,835 are also employable herein for adding the compounds to emulsions.
The organic solvent to be used in the present invention to dissolve the methine dyes includes, for example, methyl alcohol, ethyl alcohol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, benzyl alcohol, fluorine-containing alcohol, methyl cellosolve, acetone, pyridine, and their mixed solvents.
When the methine dye of the present invention is dissolved in water, or in the organic solvent as above, or in their mixed solvent, it is desirable to add a base thereto. The base may be any of organic bases or inorganic bases, including, for example, amine derivatives (e.g., triethylamine, triethanolamine), pyridine derivatives, sodium hydroxide, potassium hydroxide, sodium acetate, and potassium acetate. One preferred method of dissolving the sensitizing dye in such a solvent comprises adding the dye to a mixed solvent of water and methanol followed by adding thereto triethylamine of which the amount is equimolar to that of the dye.
The silver halide grains to be in the silver halide emulsions for use in the present invention may be any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver iedochloride and silver chloroiodobromide. For color print paper, preferred are silver chloride emulsions or silver chlorobromide emulsions for rapid and simplified processing. More preferred are emulsions in which at least 95 mol % of grains are of silver chloride (including silver chloride, silver bromochloride, silver chloroiodobromide). For shortening the time for development, especially preferred is silver chlorobromide or silver chloride substantially free from silver iodide. For color films (negative and reversal films), preferred are silver bromide emulsions or silver iodobromide emulsions. More preferred are emulsions in which at least 95 mol % of grains are of silver bromide (including silver bromide, silver iodobromide, silver chloroiodobromide).
Preferably, the mean grain size of the silver halide grains of the silver halide emulsions for use in the present invention is from 0.1 to 2 m. The grain size corresponds to the diameter of the circle of which the area is equivalent to the projected area of the grain, and the number average of the grain sizes thus actually measured is the mean grain size.
Regarding the grain size distribution thereof, the silver halide grains are preferably mono-dispersed to have a grain size distribution variation coefficient (this is obtained by dividing the standard deviation of the grain size distribution by the mean grain size) of 20% or less, more preferably 15% or less, further more preferably 10% or less. For broadening the latitude of the photographic material in processing it, it is also desirable that the mono-dispersed emulsions are blended to form one layer, or are coated to from two or more layers.
Regarding the shape of the silver halide grains in the photographic emulsions, the grains may have a regular crystal shape of, for example, cubic, octahedral or tetradecahedral grains, or may have an irregular crystal shape of, for example, spherical or tabular grains, or may be mixtures of such regular crystals and irregular crystals. Preferably, regular crystal grains account for at least 50%, more preferably at least 70%, even more preferably at least 90% of all the silver halide grains in the emulsion for use in the present invention.
The emulsions for use in the present invention may be prepared, for example, according to the methods described in P. Glafkides"" Chimie et Phisique Photographique (Paul Montel, 1967); G. F. Duffin""s Photographic Emulsion Chemistry (Focal Press, 1966); V. L. Zelikman et al""s Making and Coating Photographic Emulsion (Focal Press, 1964). Briefly, they may be prepared in any of acid method, neutral method or ammonia method. For reacting a soluble silver salt with a soluble halide to prepare an emulsion, employable is any of single-jet method or double-jet method or their combination. Also employable is a reverse-mixing method in which the grains are formed in a silver ion-rich atmosphere. One example of the double-jet method is a controlled double-jet method in which the pAg of the liquid phase where silver halide grains are formed is kept constant. According to this method, the silver halide grains formed may have a regular crystal shape and an almost uniform grain size.
The emulsions for use in the present invention are preferably so designed that at least 50%, more preferably at least 70%, even more preferably at least 80% of all the projected area of the silver halide grains in the emulsions are tabular grains having an aspect ratio of at least 2. More preferably, the aspect ratio of the tabular grains falls between 4 and 1000, further more preferably between 6 and 500, still more preferably between 8 and 300, most preferably between 15 and 200. For example, for color print paper, preferred are tabular silver chlorobromide grains; and for color films, preferred are tabular silver iodobromide grains.
One tabular grain generally has two parallel planes, and its xe2x80x9cthicknessxe2x80x9d is represented by the distance between the two parallel planes thereof. On the other hand, the diameter of one silver halide grain corresponds to the diameter of the circle of which the area is equivalent to the projected area of the grain, and the ratio of diameter/thickness of the grain is called the aspect ratio of the grain.
Tabular silver chlorobromide grains for color print paper are described in detail. Preferably, they are silver chloride-rich grains (i.e., high silver chloride grains) having a silver chloride content of at least 80 mol %, more preferably at least 95 mol %.
Also preferably, the silver chlorobromide grains are core/shell grains in which the shell portion (outermost layer) contains an iodide and its iodide content is higher than that of the core. Preferably, at least 90% of the core is silver chloride. The core portion may have two or more different halogen compositions. Preferably, the shell portion accounts for 50% or less, more preferably 20% or less of the overall volume of the core/shell grain. Also preferably, the silver iodide content of the shell portion falls between 0.5 and 13 mol %, more preferably between 1 and 6 mol %. Also preferably, the overall silver iodide content of the whole grain falls between 0.1 and 5 mol %, more preferably between 0.1 and2 mol %. Also preferably, the silver iodide content of the core portion is 1 mol % or less, more preferably 0%.
The silver bromide content may differ between the core portion and the shell portion of the grain. Preferably, the silver bromide content of the grain falls between 0 and 20 mol %, more preferably between 0.1 and 5 mol % of the overall amount of silver in the grain.
Preferably, the diameter of the silver chloride-rich tabular grain falls between 0.2 and 1.0 xcexcm; the thickness thereof is preferably 0.2 xcexcm or less, more preferably 0.15 xcexcm or less, further more preferably 0.1 xcexcm or less; and the aspect ratio thereof preferably falls between 3 and 20, more preferably between 5 and 15.
Regarding their grain size distribution, the silver chloride-rich tabular grains may be poly-dispersed or mono-dispersed, but are preferably mono-dispersed. Also preferably, the grain size distribution coefficient of the grains falls between 5 and 25%, more preferably between 5 and 20%.
Also preferably, the grain thickness distribution coefficient falls between 5 and 25%, more preferably between 5 and 15%.
In case where silver chloride-rich tabular grains for color print paper are specifically so designed that their outer surfaces are of {111} faces, a crystal phase-controlling agent is used. Such tabular grains are completed by forming two parallel twin-crystal faces, and the twin-crystal face formation depends on the ambient temperature, the dispersion medium (gelatin) and the halogen concentration, of which, therefore, the conditions must be suitably determined. For example, when a crystal phase-controlling agent is present in the system during nuclei formation therein, the gelatin concentration preferably falls between 0.1 and 10%. The chloride concentration is preferably at least 0.01 mol/liter, more preferably at least 0.03 mol/liter.
The details of the crystal phase-controlling agent and the method of using it for forming silver chloride-rich {111} tabular grains are described in JP-A 2000-29156, which is hereby incorporated by reference.
The tabular grains for use in the present invention may also be those of which the main plane is {100} face. Regarding its geometric morphology, the main plane of the tabular grains maybe in any form of rectangles, or triangles to pentagons derived from rectangles by deleting any one of four angles of rectangles (the deleted part is a right triangle of which the vertex is the deleted angle of the rectangle, and the two legs extending from the vertex forms the right triangle), or quadrilaterals to octagons derived from rectangles by deleting from 2 to 4 angles of rectangles.
Methods for forming {100} tabular silver halide grains are described, for example, in JP-A 6-301129, JP-A 6-347929, JP-A 9-34045, JP-A 9-96881, JP-A 8-122954 and JP-A 9-189977.
Regarding their halogen composition, tabular silver iodobromide grains for color films are preferably of silver iodobromide, silver iodochloride or silver iodochlorobromide having a silver iodide content of 30 mol % or less. More preferably, they are of silver iodobromide or silver iodochlorobromide having a silver iodide content of from 2 to 10 mol %. They may contain silver chloride, but their silver chloride content is preferably 8 mol % or less, more preferably 3 mol % or less, further more preferably 0 mol %.
Preferably, the diameter of the tabular silver iodobromide grains falls between 0.3 and 5.0 xcexcm, and the thickness thereof falls between 0.05 and 0.5 xcexcm. Also preferably, the aspect ratio of the tabular grains falls between 4 and 50, more preferably between 5 and 30, further more preferably between 6 and 25.
The silver halide emulsions for use in the present invention are generally subjected to chemical sensitization. The chemical sensitization includes gold sensitization with a gold compound (e.g., as in U.S. Pat. Nos. 2,448,060, 3,320,069); sensitization with metal of, for example, iridium, platinum, rhodium or palladium (e.g., as in U.S. Pat. Nos. 2,448,060, 2,566,245, 2,566,263), sulfur sensitization with a sulfur-containing compound (e.g., as in U.S. Pat. No. 2,222,264), selenium sensitization with a selenium compound, tellurium sensitization with a tellurium compound, and reduction sensitization with any of tin salts, thiourea dioxide orpolyamines (e.g., as in U.S. Pat. Nos. 2,487,850, 2,518,698, 2,521,925). These sensitizations may be effected individually or as combined.
Preferably, the emulsions for use in the present invention are chemically sensitized with a selenium sensitizer. For the selenium sensitizer, usable are known selenium compounds such as those disclosed in laid-open or published patent specifications. Concretely, in general, a labile selenium compound and/or a non-labile selenium compound are added to an emulsion and stirred at high temperature, preferably at 40xc2x0 C. or higher for a predetermined period of time to sensitize the emulsion. For the labile selenium compound, for example, preferred are those described in JP-B 44-15748, JP-B 43-13489, JP-A4-25832,and JP-A4-109240. Examples of the labile selenium sensitizer are isoselenocyanates (e.g., aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenamides, selenocarboxylic acids (e.g., 2-selenopropionic acid, 2-selenobutyric acid), selenoesters, diacylselenides (e.g., bis(3-chloro-2,6-dimethoxybenzoyl)selenide), selenophosphates, phosphine selenides, colloidal metal selenium.
Some preferred examples of labile selenium compounds usable herein are mentioned above, but these are not limitative. Anyone skilled in the art has a general understanding that the structure of labile selenium compounds that serve as sensitizers for photographic emulsions is of little importance so far as selenium in the compounds is labile and that the organic part of selenium sensitizer molecule has no other function than carries selenium to make it exist in emulsions while kept labile therein. In the present invention, any and every labile selenium compound of such a broad and generic concept is favorably used for sensitizer for emulsions.
Non-labile selenium compounds are also usable in the present invention, and their examples are described in, for example, JP-B 46-4553, JP-B 52-34492 and JP-B 52-34491.
Concretely, non-labile selenium compounds usable herein are selenious acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diarylselenides, diaryldiselenides, dialkylselenides, dialkyldiselenides, 2-selenazolidinedione, 2-selenoxazolidinethione, and their derivatives.
For selenium compounds for use herein, especially preferred are those of formulae (VII) and (VIII) in JP-A11-15115.
The selenium sensitizer may be dissolved in water or in an organic solvent of, for example, methanol or ethanol alone or in a mixed solvent of such solvents, and added to emulsions that are to be chemically sensitized. Preferably, it is added to emulsions before the start of chemical sensitization of emulsions. The selenium sensitizer to be used is not limited to only one type, but two or more different types of selenium sensitizers may be combined for use herein. Preferably, an labile selenium compound is combined with a non-labile selenium compound.
The amount of the selenium sensitizer to be added to emulsions varies, depending on the activity of the selenium sensitizer, the type and the size of silver halide to be in emulsions, and on the ripening temperature and time. Preferably, it is at least 1xc3x9710xe2x88x928 mols, more preferably from 1xc3x9710xe2x88x927 to 5xc3x9710xe2x88x925 mols per mol of silver halide in emulsions. The temperature for chemical sensitization with the selenium sensitizer is preferably 45xc2x0 C. or hither, more preferably from 50 to 80xc2x0 C. The pAg and the pH for selenium sensitization are not specifically defined, and may be determined in any desired manner. For example, the pH may vary within a broad range of from 4 to 9 to attain the object of the present invention.
Various compounds and their precursors may be added to the silver halide emulsions for use in the present invention for preventing the photographic material from being fogged while it is fabricated, stored or processed and for stabilizing the photographic properties of the photographic material. Specific examples of such compounds are described, for example, on pp. 39-72 of JP-A 62-215272 mentioned above, and they are preferred for use in the present invention. In addition, also preferred for use herein are 5-arylamino-1,2,3,4-thiatriazole compounds (in which the aryl residue has at least one electron-attracting group) such as those described in EP 0447647.
The silver halide emulsion prepared according to the present invention is applicable to both color photographic materials and black and white photographic materials. Typical examples of color photographic materials are color print paper, color negative films and color reversal films; and typical examples of black and white photographic materials are X-ray films, ordinary photographic films, and films for printing plates.
Regarding the method for formulating the photographic emulsions for use in the present invention, for example, referred to is the disclosure in JP-A 10-239789, from column 63, line 36 to column 65, line 2.
Regarding additives such as color couplers and others to the photographic material of the present invention, as well as the type of the photographic material and the mode of processing it, for example, referred to is the disclosure in JP-A10-239789, from column 65, line 3 to column 73, line 13.
Various additive such as those mentioned hereinabove may be used in the silver halide photographic material of the present invention. In addition to these, any other various additives may also be in the material in accordance with their object.
These additives are described in more detail in Research Disclosure, Item 17643 (December 1978), ibid., Item 18716 (November 1979), and ibid., Item 308119 (December 1989), as listed in the following Table.
Other various techniques relating to emulsions for use in the present invention and emulsion layer configuration in fabricating photographic materials, as well as other silver halide emulsions, dye-forming couplers, functional couplers such as DIR couplers, other various additives and development of photographic materials are described in EP 0565096A1 (laid-open on Oct. 13, 1993) and in other patent publications refereed to in that EP publication. The technical matters and the parts of the EP publication that disclose them are listed in the following Table.